EP0711743B2 - Polyol compositions, process for their preparation and their applications - Google Patents

Description

The present invention relates to a new polyol composition having a very high thermal stability and a very high chemical stability in an alkaline medium and a very low reactivity.

It also relates to a process for preparing this novel composition and its applications, in particular its use for the preparation of dentifrices.

The term "polyols" in the present invention refers to the products obtained by catalytic hydrogenation of simple reducing sugars, but also of more complex reducing sugars composed of higher homologues of these simple sugars, such as disaccharides, oligosaccharides and polysaccharides, and their mixtures.

Generally, the simple reducing sugars intended for catalytic hydrogenation for obtaining the polyol compositions of the type of those of the invention are glucose, xylose, fructose and mannose. The polyols obtained are then sorbitol, xylitol and mannitol.

The disaccharides are most often maltose, isomaitulose, maltulose, isomaltose and lactose, which lead, by hydrogenation, to maltitol, isomalt, isomaltitol and lactitol.

Oligosaccharides and polysaccharides, which are higher molecular weight products, are usually derived from acidic and / or enzymatic hydrolysis of starches and / or starches, xylans or fructans such as inulin, but may also be be obtained by acidic and / or enzymatic recombination of mono or disaccharides such as those mentioned above.

By polyol composition is meant in the present invention mixtures of polyols which form syrups incristallizable at 20 ° C and a dry matter of 70% when stored in an airtight container during a month of storage . Some of these syrups can even form organic glasses, such as boiled sugars, resistant to crystallization.

The confectionery, pharmacy, oral hygiene and even the chemical industries commonly use polyol compositions in the manufacture of, for example, sugar-free candies, acidic or antitussive syrups, toothpastes, polyurethane foams.

Sorbitol syrups obtained by hydrogenation of glucose or starch hydrolysates of variable but high glucose content represent a very important class because of their economic weight. These syrups are primarily used as substitutes for sugars. Their sweet taste makes it possible to prepare many low-calorie and little or no cariogenic products such as certain confectioneries or such as certain pharmaceutical syrups.

Sorbitol syrups are used second because of their excellent wetting power. Such uses are widely described in: "SORBITOL", F. Baudart, Ed DUNOD (1971), p. 19 to 75. This is the case in the manufacture of toothpastes, creams and cosmetic milks, shaving foams but also food products such as pastries and pastries and other products such as tobacco or paper. In these fields, sorbitol syrups are preferably used, or rather non-crystallizable or hardly crystallizable polyol compositions because it is the property of humectancy, which alone is imparted in the state of solutes.

Third, other uses of sorbitol syrups take advantage of the plasticizing properties of sorbitol. This is the case in the industry of glues, biodegradable plastics, or in the chewing gum industry.

Fourthly, finally, sorbitol syrups are sometimes used as chemical intermediates in the manufacture of, for example, sorbitan esters or initiators for the manufacture of polyurethane foams and alkyd resins. In this case, it is the chemical properties of the polyols that are used.

Maltitol syrups, obtained by catalytic hydrogenation of starch hydrolysates of varying richness in maltose, also represent an important class among the polyol compositions. They are today mainly used because of their high sweetening power to prepare, as with the aid of sorbitol syrups, non-cariogenic food and pharmaceutical products. It has been envisaged to use them also as chemical intermediates to prepare surfactants and to enter the composition of polyurethane foams.

Xylitol syrups, representing a third class of polyol compositions, are to date products in full development. Although more expensive than sorbitol or maltitol syrups, it is proposed to use them in the same applications as those mentioned above due in particular to their very high sweetening power and their excellent humectant properties.

The industry also employs other polyol compositions. Hydrogenated glucose syrups rich in oligo and polysaccharides thus find application in the field of foundry, metal quenching or detergency. Such applications are described in patents FR 2,348,771 and EP 100,280.

Other syrups based on oligo and hydrogenated polysaccharides, obtained by acid and / or enzymatic recombination of glucose or maltose in particular, are beginning to be used in industry. It is, for example, hydrogenated polydextrose which is accepted to be advantageously used in the food industry as a very low-calorie load-bearing agent, particularly in the manufacture of beverages, frozen products and confectionery. This is particularly described in US Patents 3,766,165 and US 3,876,794.

It is known that the applications of the polyol compositions are however limited in certain sectors of the industry in that these compositions do not fully satisfy the constraints of thermal stability and stability in an alkaline medium or of reactivity with regard to a few specific substances (Dunod, 28).

There is thus a phenomenon of yellowing at high temperature of these compositions when they are used in the manufacture of boiled sugars. Such a coloration is often incompatible with certain flavors of candy.

In the manufacture of alkaline toothpastes, pastes in which crystals of carbonate or of sodium phosphate are used, it is preferred to employ other products which are less economical than polyol compositions, such as glycols, propanediols or glycerol. . Because, the polyol compositions take in these products a brown color over time.

In the manufacture of certain quality tobaccos, it is also preferred to use glycerine because of the parasitic tastes conferred by the polyol compositions, although their humectant properties are considered superior.

It also happens that these polyol compositions are discarded from the manufacture of surfactants, polyurethane foams, detergents, detergents and pharmaceutical acid syrups because of the yellowish or even brown color which they confer. to these products, although again, they satisfy all the other technical constraints related to these applications (DUNOD, p.75).

There is therefore at present a need to have polyol compositions thermally and chemically more stable than those available on the market.

However, it is to the merit of the Applicant Company to have discovered that polyol compositions consisting of polyol mixtures which form incristallizable syrups have satisfactory stability conditions since their optical density, measured in an S test, is internal. or equal to 0.100.

The S test is based on a spectrophotometric measurement applied to the products to be tested.

• on amène, si besoin est, par concentration ou par dilution aqueuse le sirop de polyol à tester à une matière sèche de 40 % en poids,
• on ajoute à 5ml de celle solution 500mg d'hydrogénocarbonate de sodium de qualité ultrapure, vendu par exemple sous le nom RP NORMAPUR™ pour analyses par la société PROLABO, 65 Bd Richard Lenoir, PARIS, FRANCE, et 250mg d'une solution aqueuse à 20 % d'ammoniac,
• on mélange l'ensemble et on le chauffe pendant 2 heures au bain-marie à 100°C sans imposer d'agitation,
• on amène la solution à 20°C et on mesure la densité optique de la solution ainsi obtenue à une longueur d'onde de 420 nm grâce à un spectrophotomètre tel que celui commercialisé par PERKIN-ELMER sous la marque Lambda 5 UV/VIS Spectrophotometer. Grâce à cet appareil, à titre d'exemple, on obtient des densités optiques de 0,040, 0,080 et 0,120 en remplaçant les 5 ml de solution de polyols à 40 % de matière sèche par 5 ml d'une solution contenant respectivement 40, 80 et 120 parties par million de D⁺ glucose anhydre RP NORMAPUR™ pour analyses (société PROLABO), dissous dans de l'eau distillée.

To conduct this test S, proceed as follows:

• if necessary, the polyol syrup to be tested is brought to concentration by concentration or by aqueous dilution at a solids content of 40% by weight,
• 5 ml of this solution is added 500 mg of sodium hydrogencarbonate of ultrapure quality, sold for example under the name RP NORMAPUR ™ for analysis by the company PROLABO, 65 Bd Richard Lenoir, PARIS, FRANCE, and 250 mg of an aqueous solution. 20% ammonia,
• the mixture is mixed and heated for 2 hours in a water bath at 100 ° C. without imposing agitation,
• the solution is brought to 20 ° C. and the optical density of the solution thus obtained is measured at a wavelength of 420 nm using a spectrophotometer such as that marketed by PERKIN-ELMER under the trademark Lambda UV / VIS Spectrophotometer. With this apparatus, for example, optical densities of 0.040, 0.080 and 0.120 are obtained by replacing the 5 ml of polyol solution with 40% solids by 5 ml of a solution containing respectively 40, 80 and 120 parts per million of D ⁺ NORMAPUR ™ RP anhydrous glucose for analysis (PROLABO company), dissolved in distilled water.

The polyol composition is all the more stable as the value measured in the test S is low.

As verified by the applicant, it should be noted that, surprisingly and unexpectedly, there does not seem to be a correspondence between the richness of the polyol compositions in a particular polyol, or their content of reducing sugars residual or free (measured according to the usual method cupro-tartro-sodium of Bertrand or the method using dinitrosalicylic acid) and the result obtained in the test S on the other hand.

In other words, there does not seem to be a direct link between the thermal and chemical stability of a polyol composition and its content of residual reducing sugars.

This could be explained by the fact that by the S test an overall measurement is obtained and that the coloration obtained in this test probably depends at the same time on the final pH of the syrup, the quantity of minerals present in the syrup, the nature of these minerals, the amount of reducing functions not reduced by hydrogenation, as well as the nature of the molecules bearing these unreduced functions: monosaccharides, disaccharides, oligo or polysaccharides.

Thus, for example, it is observed in test S that, surprisingly, traces of unresolved oligo- and polysaccharides generate, all things being equal, more intense colorations than do mono- and disaccharides which are not reduced. at the same concentration of reducing functions.

Thus, 180 parts per million (ppm) of dextrose are less prone to staining in a basic medium than 342 ppm of maltose expressing the same reducing power, which themselves stain less than higher concentrations of oligosaccharides or polysaccharides. expressing the same reducing power.

Such a finding suggests that it would be necessary and sufficient, in order to obtain polyol compositions according to the invention - especially when they contain a lot of oligo and reduced polysaccharides - to continue longer than usual. catalytic hydrogenation, so as to obtain levels of residual or free reducing sugars at the limit of the analytical detection.

The catalytic hydrogenation of glucose or glucose syrups, as well as that of fructose or xylose, as commonly practiced, is described, for example, in "CHEMICAL CONVERSION OF STARCH BASED GLUCOSE SYRUPS, chap. 9, p. 281, "Starch Conversion Technology", 1985, Vol 14 by APG KIEBOOM and H. VAN BEKKUM.

The Applicant Company however noted that on the one hand it was not necessary to unreasonably prolong the catalytic hydrogenation in order to obtain the composition according to the invention and that on the other hand such prolongation of the hydrogenation did not allow to obtain said composition.

It appears that di-, oligo-, and polysaccharides are more difficult to completely hydrogenate than monosaccharides.

After many works, the Applicant has found that it was appropriate, in order to obtain the compositions according to the invention, to add at least one additional step called "stabilization" to conventional catalytic hydrogenation processes. This stabilization step may consist, for example and without being limiting, in a fermentation, oxidation or caramelization step.

The stabilization step makes it possible to obtain a polyol composition having an optical density less than or equal to 0.100 in the S test. This step must be placed after the hydrogenation step and preferably before the final purification step. the polyol composition.

The invention thus relates first of all to the use for the preparation of dentifrices of a polyol composition consisting of mixtures of polyols which form incressallizable syrups and characterized in that it has an optical density less than or equal to 0.100 in the S test. Preferably, the polyol composition used according to the invention having an optical density less than or equal to 0.100 in the test S, comprises, relative to its content of polyols in the dry state. , a content of 0.01 to 95% of hydrogenated monosaccharides and / or hydrogenated disaccharides, the complement to 100% of the polyols consisting of hydrogenated oligomers and polysaccharides, these contents being expressed relative to the dry matter of polyols present.

The hydrogenated monosaccharides may advantageously be chosen from the group comprising sorbitol, iditol, mannitol, xylitol, arabitol and erythritol, and more preferably from sorbitol, mannitol and xylitol.

The hydrogenated disaccharides may be advantageously chosen from the group comprising maltitol, hydrogenated maltulose, hydrogenated isomaltulose or isomalt (a mixture of glucopyranosido-1,6-mannitol and glucopyranosido-1,6-sorbitol), isomaltitol, lactitol, hydrogenated inulobiosis, and more preferentially among maltitol, lactitol and hydrogenated isomaltulose.

The hydrogenated oligosaccharides and polysaccharides may consist of maltotriitol, maltotetretol and other hydrogenated oligo- and polysaccharides obtained by hydrolysis of the starch followed by hydrogenation. Said hydrogenated oligosaccharides and polysaccharides may, however, also consist of cellobiitol, cellotriitol, xylobiitol, xylotriitol and other hydrogenated oligo- and polysaccharides obtained by hydrolysis, generally acidic, of cellulose, xylans or fructans, for example inulin. , dextrins, polyglucoses such as polydextrose, followed by hydrogenation. The said hydrogenated oligo- and polysaccharides may also come from an acidic or enzymatic recombination of mono- or disaccharides, possibly reduced, such as those mentioned above, alone or in the presence of other oligosaccharides and optionally reduced polysaccharides, followed by a hydrogenation. The hydrogenated oligosaccharides and polysaccharides which are preferred to be present in the composition are oligo- and polysaccharides derived from hydrogenated hydrolysates of starches, dextrins and hydrogenated polyglucoses, optionally hydrolysed beforehand.

The content of mono- and disaccharides of the polyol composition according to the invention is more preferably between 0.1 and 90%, more preferably between 0.5 and 86% and more preferably between 50 and 86% of the polyols, said contents being expressed. relative to the dry matter of the polyols present in the composition; the content of hydrogenated oligo- and polysaccharides representing the complement to 100% of this dry matter. Thus, it is advantageous to obtain, for certain applications, a composition which is less prone to the crystallization of one or other of these hydrogenated mono- or disaccharides.

In order to best suit those jobs where the constraints in terms of taste, thermal or chemical stability are the most drastic, the polyol composition consisting of mixtures of polyols which form incristallizable syrups used in accordance with the invention preferably has a optical density less than or equal to 0.075, more preferably less than or equal to 0.060, and more preferably less than or equal to 0.040 in the S test. It may be noted here that these optical density values, which characterize the polyol composition in accordance with The invention is very substantially lower than the values found for the polyol compositions described or marketed to date. Indeed, for these latter products, the optical density in the same test S is always much greater than 0.100 and generally between 0.500 and 0.850.

The polyol composition consisting of mixtures of polyols which form incristallizable syrups used in accordance with the invention, depending on whether it is more or less rich in mono- and disaccharides, has a total sugar content after total hydrolysis according to the Bertrand method. between 3.5 and 98%, preferably between 6 and 92% and more preferably between 8 and 90%, this content being expressed relative to the dry matter of the composition.

The polyol composition consisting of mixtures of polyols which form incristallizable syrups used in accordance with the invention may be presented in the form of syrup or powder, depending on the subsequent purpose reserved for it. It can also, given its very high stability and high compatibility with the vast majority of ingredients or additives used in industry, be mixed with the most diverse products. In particular, glycols such as ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol and polyethylene glycols, glycerol or propanediols can be added without any disadvantage to the composition of the invention in order to adjust the properties of the composition or to present it in the form of a syrup with a very high dry matter, that is to say up to 96% of dry matter.

The invention relates secondly to a process for preparing a stable polyol composition.

• une étape de stabilisation telle qu'une fermentation, une oxydation ou une caramélisation, visant à amener la densité optique du sirop hydrogéné à une valeur inférieure ou égale à 0,100, de préférence inférieure ou égale à 0,075 et plus préférentiellement encore inférieure ou égale à 0.060 dans le test S.
• une étape de purification du sirop hydrogéné "stabilisé" ainsi obtenu.

This process is characterized in that a syrup of polyols obtained by catalytic hydrogenation of simple or complex reducing sugars is subjected to the succession of the following stages:

• a stabilization step such as a fermentation, an oxidation or a caramelization, aimed at bringing the optical density of the hydrogenated syrup to a value less than or equal to 0.100, preferably less than or equal to 0.075 and still more preferably less than or equal to 0.060 in the S test.
• a purification step of the "stabilized" hydrogenated syrup thus obtained.

It goes without saying that the process according to the invention may comprise other conventional steps known to those skilled in the art, such as, in particular, purification steps on earth, activated carbon and / or resins, concentration and possible drying. .

The stabilization step is preferably carried out on a demineralized hydrogenated syrup, in order to remove any traces of soluble nickel or other hydrogenation catalysts.

It is preferred to subject to the process according to the invention a polyol syrup obtained by catalytic hydrogenation of simple or complex reducing sugars until a percentage of residual reducing sugars of less than 0.50% is obtained, measured according to the Bertrand method. . This percentage is more preferably less than 0.25% and more preferably still less than 0.20%.

It is also preferred to use a demineralised polyol syrup, especially in the case where the stabilization step consists of a fermentation or enzymatic oxidation treatment.

Thus it is preferred to use as a product intended for the stabilization stage, but without this being necessarily imperative, a syrup of polyols having an optical density of preferably less than or equal to 0.200, more preferably less than or equal to at 0.170, and more preferably still less than or equal to 0.150 in the S test.

According to a first possibility, the stabilization step consists of an enzymatic oxidation step by using a glucose oxidase. Preferably, this enzymatic oxidation is carried out in the presence of catalase.

Glucose oxidase catalyzes the following reaction:

Glucose + O ₂ + H ₂ O → Gluconic Acid + H ₂ O ₂

Catalase transforms the oxygenated water thus produced according to the reaction:

H ₂ O ₂ → H ₂ O + 1/2 O ₂

Such an enzymatic composition is for example available from the company NOVO, DA-NEMARK under the name SP 358.

This enzymatic oxidation must take place in an aerated medium and the pH of the medium is maintained at a value of between 3.5 and 8.0, preferably between 4.0 and 7.0 and even more preferably between 5.0 and 6. , 0.

The concentration of the hydrogenated syrup, preferably demineralized, is not critical and can vary from 5 to 75%. However, high concentrations may require working by regulating the pH using a base or performing the oxidation in the presence of a buffering salt such as calcium carbonate. Stabilizing the pH to between 5.0 and 6.0 is preferable.

For economic reasons, however, it is preferred to carry out the oxidation on aqueous solutions containing about 30 to 50% solids. The temperature can be adjusted in a wide range of 15 to 70 ° C but for convenience it is preferred to work at 30 - 40 ° C, temperatures at which the enzyme is most active.

A convenient material for performing this oxidation is an aerobic fermentor, although it is not necessary for this step to take place under sterile conditions or even rigorous aseptic. The amount of enzymes used is such that the oxidation takes place in 0.5 to 24 hours.

This enzymatic oxidation step, in the presence or absence of catalase, must be followed by a demineralization step on anion exchanger in hydroxyl OH- form, so as to eliminate the acids formed by the action of the enzyme.

It is preferred to use as anion exchanger a strong anionic resin which makes it possible to efficiently bind both the weak acids that are gluconic acid or other glucose oxidation acids which may have appeared, and the acids sometimes present from inherent way in the hydrogenated product like citric acid in the case of hydrogenated polydextrose.

The preferred resins are those bearing functional groups of the quaternary amine type and preferably quaternary trimethylamine groups, such as the AMBERLITE IRA 900 resin marketed by ROHM and HAAS.

These resins are used in their hydroxyl form or strong OH- base.

To increase their regeneration efficiency with alkalis, it may be preferred to couple them with a weak anionic resin essentially carrying tertiary amine groups such as AMBERLITE IRA 93 from the same company.

According to a second possibility, the stabilization step consists of a chemical oxidation step. Preferably, this chemical oxidation is carried out in the presence of methylene blue, hydroquinone or resorcinol in order to catalyze the reactions and to increase the oxidation yields. It is possible to proceed in a known manner for reducing sugar syrups, for example by following the SPENGLER-PFAN-NENSTIEL process described in the memoir of DUBOURG and NAFFA (Bull Soc.Child Inc. (1959) 1353-1362). After oxidation, the syrup must be purified according to the same techniques as those mentioned above for the enzymatic oxidation.

According to a third possibility, the stabilization step is a fermentation step. The faculty of certain microorganisms, for example certain yeasts, is then used to metabolize simple sugars and not polyols and to transform them for example into ethanol and carbon dioxide. It is necessary to do this to add to the syrup a nitrogen source such as for example yeast extracts. It goes without saying that the fermentation conditions must be adjusted according to the type of microorganism chosen.

However, it is preferred to retain microorganisms both osmophilic and thermophilic, so that for reasons of cost, can work at high dry matter and at a high temperature.

It is also preferred to select, for the purpose of facilitating subsequent purification, non-producing microorganisms of secondary metabolites. Only then carbon dioxide or organic acids are produced.

After fermentation, the biomass produced must be removed, for example by decantation, centrifugation or filtration, before further purification of the polyol syrup. Heating to 80 ° C makes it possible to eliminate the ethanol that may be produced, whereas treatment with anion exchange resins is useful for removing acids that may have formed during the fermentation.

According to a fourth and last method, the stabilization step consists of an alkaline degradation step or caramelization step.

It is preferred to work at an alkaline pH of between 8 and 12 and preferably hot so as to shorten the reaction times. Caramelization products, consisting essentially of acids, can be removed by passage through resins.

The process according to the invention makes it possible to obtain polyol compositions of unmatched thermal and chemical stability to date, and this at an acceptable cost.

Of course, in all cases, the organoleptic properties and the residual color of the products obtained can be further improved by complementary treatments using, for example, animal or vegetable black.

One of the main merits of the present invention is to provide a very stable polyol composition that does not generate undesirable flavors or colorings under a wide variety of application conditions. The invention thus relates in third place to the use of said polyol composition. This composition can be used as a sweetening agent, a texturizing agent, a complexing agent, a humectant or a plasticizer in a large number of products. It can advantageously, given its total compatibility with a large number of ingredients and additives usually used in industry, be associated or mixed with preservatives, emulsifiers, flavors, sugars, intense sweeteners, bases, pharmaceutical or veterinary active ingredients, fats, inorganic or organic fillers such as polydextrose, fibers, fructooligosaccharides, gums, organic or inorganic gelling agents such as proteins, pectins, modified celluloses, extracts of algae and seeds, bacterial polysaccharides, silicas.

The polyol composition according to the invention may be suitable for the preparation of products intended to be ingested by humans or animals but also to be used in the formulation of hair products or dermal application. It can also be used in the detergent, tobacco or plastics industry. These products, in which the polyol composition is usable, may have a liquid or viscous texture: this is the case for example with drinks, syrups, emulsions, suspensions, elixirs, mouthwashes, drinkable ampoules. , dishwashing liquids. They may also have a pasty texture, such as anti-acid products or non-crystallized or semi-crystallized confectionery products such as sweets, jellies, gums, chewing pastes, caramels, chewing gums, forages , the cereal bars. They can also have a gelled texture, as is the case of food gels such as puddings, jams, jellies, dairy desserts, pharmaceutical and veterinary gels, or toothpastes. Finally, they can have a solid texture, as in pastry products, biscuits, breadmaking, tablets, desserts, atomized or extruded powders of sweeteners or flavors, lyophilisates pharmaceutical or veterinary products, tobaccos and powders for washing clothes or dishes.

The composition according to the invention is particularly recommended for preparing all types of products manufactured in the presence of alkalis, such as polyurethane foams, or containing alkaline agents, such as antacids, detergents, shaving foams. depilatory creams, and dentifrices based for example on carbonate or sodium phosphate. It is also especially recommended for preparing products that are processed or obtained at very high temperatures. This is the case for example cooked sugars.

Another advantage of the polyol composition according to the invention is that it is particularly stable with regard to the enzymes of microorganisms or vis-à-vis the flavors.

The examples which follow, and which are given in a non-limiting way, will better illustrate the invention.

Example 1

A polyol composition according to the invention is prepared from a sorbitol syrup marketed by the applicant under the brand name NEOSORB®70 / 70. This syrup has an optical density in the S test close to 0.600.

By dilution, this syrup is brought to a dry matter of 40%. The solution obtained is subjected to the action of glucose oxidase at a rate of 70 GOX units of glucose oxidase SP 358 per kilogram of dry substrate. This reaction is carried out in aerated tanks at a rate of 1.5 volumes of air per volume of solution per minute, at a pH regulated at 5.0 by progressive addition of sodium hydroxide.

It is carried out at 35 ° C. for 16 hours, after which the solution is treated on a battery of ion exchange resins comprising in series a strong cationic resin IR 200 C and then a strong anionic resin IRA 900.

Under these conditions, there is obtained a polyol composition having a very clearly lowered optical density, close to 0.070.

Example 2

• bicarbonate de sodium    30,0 %
• composition de polyols (à 70 % MS)    36,0 %
• silice abrasive    8,0 %
• silice épaississante    5,0 %
• carboxyméthyl cellulose    0,7 %
• lauryl sulfate de sodium    1,7 %
• méthyl parabène    0,1 %
• oxyde de titane    0,7 %
• eau    17,8 %

Toothpastes are prepared according to the formulation below:

• sodium bicarbonate 30.0%
• polyol composition (at 70% DM) 36.0%
• abrasive silica 8.0%
• thickening silica 5.0%
• 0.7% carboxymethyl cellulose
• sodium lauryl sulfate 1.7%
• methyl paraben 0.1%
• 0.7% titanium oxide
• water 17.8%

A first toothpaste is made by using, as a polyol composition, the NEOSORB® 70/70 sorbitol syrup cited in Example 1 (control dentifrice).

A second dentifrice is prepared using the polyol composition according to the invention described in Example 1.

Packaged toothpastes are stored in tubes of the POLYFOIL ^R type for 10 days at 45 ° C., which corresponds to a storage period at 20 ° C. of approximately 15 months.

It is noted at the end of this period that the control dentifrice, initially white, has a light brown color.

On the other hand, the dentifrice prepared from the polyol composition according to the invention has an unchanged appearance with respect to the initial state. This is a decisive technical and commercial advantage for users.

Example 3

A thermal stability comparison test of a sorbitol syrup of the prior art sold by the applicant under the trade name NEOSORB® 70/70 and the polyol composition according to the invention obtained according to the described method is carried out. in example 1.

For this, these two syrups having a solids content of 70% are subjected to autoclaving at 117 ° C. for 20 minutes.

After the syrups have come back to room temperature, they proceed to a blind tasting by a jury of 15 people.

It is very clear that the polyol composition according to the invention is preferred, because of its very neutral taste, less metallic and almost devoid of a caramel note. This property makes the polyol composition according to the invention particularly interesting for multiple applications.

In addition, there has been a much lesser interference with certain substances and in particular with certain intense aromas and sweeteners.

Therefore, it is easier than using the syrups of the prior art, adjust the organoleptic quality of food products, toothpastes, tobacco or other.

Example 4

The reactivity with the spearmint and peppermint flavors of a sorbitol syrup according to the prior art (NEOSORB®70 / 70 described in Example 1) is compared with the reactivity with respect to the same aromas of a sorbitol composition according to the invention obtained as described in Example 1.

For this purpose, 40 parts of sorbitol syrup (art prior art or invention) are mixed with 28 parts of water and 0.8 parts of mint flavor. The mixtures are stored in sealed containers for 7 days at 20 ° C, 40 ° C and 60 ° C.

• en ce qui concerne le sirop de sorbitol de l'art antérieur, les échantillons maintenus à 20°C avec les arômes de spearmint ou de peppermint ont un goût mentholé bien préservé mais aussi un mauvais arrière-goût, les échantillons maintenus à 40°C ont une aromatisation mentholée dégradée, et les échantillons maintenus à 60°C n'ont plus de goût mentholé mais un goût complètement modifié,
• en ce qui concerne la composition de polyol selon l'invention, aucune modification en goût n'est notée à 20°C et 40°C et seulement une légère modification est perçue à 60°C.

It appears after this period, according to the results obtained by a panel of 15 people, that:

• as regards the sorbitol syrup of the prior art, the samples kept at 20 ° C. with the aromas of spearmint or peppermint have a well-preserved mint flavor but also a bad aftertaste, the samples kept at 40 ° C. have a degraded menthol flavoring, and the samples kept at 60 ° C have no more minty taste but a completely modified taste,
• as regards the polyol composition according to the invention, no change in taste is noted at 20 ° C and 40 ° C and only a slight change is seen at 60 ° C.

By analysis of the aromas by chromatography, it appears that, after storage under the above conditions, the mixtures with the sorbitol syrup according to the prior art contain new volatile components in comparison with the flavorings used or in comparison with the mixtures containing the sorbitol composition according to the invention.

In conclusion, the sorbitol composition according to the invention has a very low reactivity to mint aromas and is therefore more interesting for the industry.

Claims (5)

1. Use, for the preparation of dentifrices, of a polyol composition which is constituted by mixtures of polyols forming syrups that are non-crystallizable at 20°C and at a solids content of 70% when they are stored in an air-tight container for a storage period of one month, having a total sugars content, after total hydrolysis according to the Bertrand method, of between 3.5 and 98% and exhibiting an optical density lower than or equal to 0.100 in an S test consisting of:

   - bringing the polyol syrup to be tested to a solids content of 40% by weight,

   - adding to 5 ml of this solution, 500 mg of sodium hydrogen carbonate of ultrapure quality and 250 mg of an aqueous solution containing 20% of ammonia,

   - mixing the whole and heating it for 2 hours on a steam bath at 100°C without stirring being applied,

   - bringing the solution to 20°C and measuring the optical density of the solution thus obtained at a wavelength of 420 nm using a spectrometer.
2. Use according to claim 1, characterized in that the polyol composition exhibits an optical density lower than or equal to 0.075, preferably lower than 0.060, and even more preferably lower than 0.040 in the S test.
3. Use according to claim 1 or claim 2, characterized in that the polyol composition has a total sugars content, after total hydrolysis according to the Bertrand method, of between 6 and 92% and preferably between 8 and 90%.
4. Use according to any one of claims 1 to 3, characterized in that the polyol composition comprises from 0.01 to 95% of hydrogenated mono- and/or disaccharides, the remainder to 100% consisting of hydrogenated oligo- and polysaccharides.
5. Use according to any one of claims 1 to 4, characterized in that in the polyol composition:

   - the hydrogenated monosaccharides are selected from the group comprising sorbitol, iditol, mannitol, xylitol, arabitol and erythritol, and preferably from sorbitol, mannitol and xylitol,

   - and the hydrogenated disaccharides are selected from the group comprising maltitol, hydrogenated maltulose, hydrogenated isomaltulose or isomalt, isomaltitol, lactitol, hydrogenated inulobiose, and preferably from maltitol, lactitol and hydrogenated isomaltulose.